TWI301928B

TWI301928B - Resist compositions with polymers having pendant groups containing plural acid labile moieties

Info

Publication number: TWI301928B
Application number: TW091108278A
Authority: TW
Inventors: Rao Varanasi Pushkara; C Lawson Margaret; Li Wenjie
Original assignee: Ibm
Priority date: 2001-04-27
Filing date: 2002-04-22
Publication date: 2008-10-11
Also published as: WO2002088077A2; WO2002088077A3; KR100553916B1; JP2004525425A; KR20040030582A; MY122873A; CN1272668C; CN1529834A; JP3928954B2; AU2002305222A1; US20020182534A1; US6534239B2

Description

1301928 A7 B7 五、發明説明（）發明背景：不管是微電子產業或其他製造微結構（例如微機械、磁阻續寫頭）的工業中，都不斷有縮小特徵尺寸的需求。在微電子產業中，其需求是縮小微電子裝置的尺寸與 /或在給定的晶片尺寸中容納更多的電路。但要製造更小的裝置，便必須在微影技術微影上有所突破，以能可靠的分辨特徵與間.隙。光學解析度部份受限於用來製造微影圖形的光（或他種輻射）波長。因此，使用短波長的光線已為微影製程的發展趨勢。最近發展的趨勢由波長為3 50nm的I線輻射轉移到波長為248nm 的輻射’為了未來更小尺寸的需求，有需要將所使用之波長再縮短為l$3nm。但不幸的是目前微影製程中供波長為24 8nm福射使用的光阻組成物，在如此短的波長照射下，會產生不穩定的現象。光阻組成物不但必須有合適的光學特質，以在需求的光波長下’能得到合適的影像解析度，該組成物尚需具有合適的化學與機械性質，使影像能從已圖案化的光阻轉移到覆蓋於其下的基材層。因此對圖形具選擇性曝光特性的正光阻，必須具有適當的溶解反應特性（例如在曝光區域中能選擇性溶解）以得到需要的光阻結構。儘管在微影技術中使用鹼性顯影劑水溶液，已經累積有相I 廣泛的經驗，但是於顯影劑溶液中進行的反應仍是決定是否能進行合適溶解反應之關鍵。第4頁本紙張尺度適用中國國家標準(CNS)A4規格(210Χ 297公釐） (請先閱讀背面之注意事項再本頁) 1·.訂· 經濟部智慧財產局員工消費合作社印製 1301928 A7 B7 五、發明説明（）圖案化的光阻結構（顯影後）必須能有足夠的抗性足-以使圖形轉移到其底下的基材層上。一般，圖形轉移是經由濕化學蝕刻或離子蝕刻的方式達成。已刻畫圖形的光阻層能否承受圖形轉移蝕刻製程，（亦即，光阻層是否在蝕刻過程中具足夠抗性）乃是該光阻組成物一項非常重要的特徵。當某些光阻組成物被設計來用於光波長為1 93 nm 的輻射時，這些組成物往往因在上述領域缺乏預期的效能表現，而無法顯現以短波長進行成像所能達到之較佳解析度的優點。雖然在上述參考文獻中所揭露之光阻組成物，已較先前技藝為進步，可將微影技術應用於波長 193 nm處，但在光波長193 nm處供微影技術使用的光阻組成物仍需改進。例如光阻組成物仍被期望有較好的顯影特性（例如解析度、顯影速度、對比、收縮現象等），較好的蝕刻抗性，與較好的微影製程範圍。尤其收縮特性上，光阻組成物最被期待能被進一步改良。發明概述：經濟部智慧財產局員工消費合作社印製本發明為關於可使微影技術具高解析度的光阻組成物，並且有（a)在曝光與/或後曝光烘烤時有較小的收縮現象；（b)較佳的溶解特性；與/或（c)較佳的配方/覆膜均— 性。且本發明組成物在1 93 nm成像輻射（或可能在其他波長的輻射）下進行成像時有較佳的成像效果。本發明尚提供使用本發明光阻組成物來創造光阻結第5頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 a7 __ B7 五、發明說明（）構之微影方法；以及以此種光阻結構將圖形轉移到所覆-蓋的基材層的方法。本發明之微影方法，在波長為193nm 之紫外光對圖形進行具選擇性曝光時，具有較佳之特性。本發明方法較佳係能解析尺寸小於1 50nm的特徵，尤其是尺寸小於 130nm且沒有使用相位移光罩下之特徵。本發明之一態樣為一種光阻組成物，其至少包含： (a) —成像聚合物，與（b) 一對光敏感的酸產生物，該成像聚合物至少包含單體單元，該單體單元係具有自單體中可聚合部分伸出之内含多元酸不穩定表位之侧基團（以下簡稱「PALM」基團）。PALM基團可能自環狀婦烴單體中伸出，或自其他可形成成像聚合物骨幹之合適的單體單元中伸出。較佳的PALM基團為具有較大體積的末端基團者，例如一脂環族基團和/或一具有中等長度碳鍊 (亦即，CpCm)之碳氫化合物。在缺乏酸產生物所產生的酸時’較佳的PALM基團係可抑制光阻組成物在鹼性水溶液中溶解。較佳是，該成像聚合物包含（i) 一在聚合物骨幹中之環狀烯蛵單體單元（亦即，組成該聚合物之單體單元中的可聚合部分）；與/或（ii)位於PALM.基團末端之具較大體積的脂環族表位。在缺乏酸產生物所產生的酸時，該成像聚合物較佳係幾乎不溶於鹼性水溶液中，這種光阻物稱為正光阻。本發明之其他態樣為含PALM之單體與内含該含第6頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再9本頁) 本一訂· 經濟部智慧財產局員工消費合作社印製 1301928 A7 B7 五、發明説明（ PALM之單體的成像聚合物。請先閲讀背面之注意事項本發明另一態樣係為一種在基材上創造一圖案化光阻結構的方法，此方法至少包含： (a) 提供一基材，其係具有一本發明光阻組成物之表層， (b) 以成像輻射光圖案化地曝曬該光阻層，使光組層之一部分被該成像輻射光曝光；及 (〇) 讓光阻層與一驗性顯影劑水溶液接觸，以移除光阻層上被曝光部分，用以創造出圖案化之光阻結構。較佳是，在上述方法之步驟（b)中，係使用波長為193 nm的紫外光。本發明尚涵蓋利用内含本發明組成物之圖案化光阻結構來製造具導電性、半導電性、磁性或絕緣結構之製程。本發明之這些及其他態樣，將詳細說明如下。發明詳細說明：經濟部智慧財產局員工消費合作社印製本發明光阻組成物之一般特徵為具有内含PALM側基團之單體單元的成像聚合物。這些組成物較佳係能以 193nm光來提供高解析度的微影圖案，並有以下特性： (a)在曝光與/或後曝光烘烤時有較小收縮現象；（b)較佳的溶解特性；與/或（c)較佳的配方/覆膜均一性。本發明更涵蓋内含本發明光阻組成物之圖案化的光阻結構，創造該光阻結構的方法；及使用該光阻結構來形成導電第頂本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 A7 B7 五、發明説明（）性、半導電性與/或絕緣結構之製程。本發明尚涵蓋具-PALM側基團之可聚合單體。本發明光阻組成物一般至少包含（a) —成像聚合物；與（b)—光敏感之酸產生物，該成像聚合物至少包含具PALM側基團之單體單元。内含PALM側基團之較佳的單體單元可以下式表示： -Μ- [ί]ρ C=0 i ①1301928 A7 B7 V. INSTRUCTIONS () BACKGROUND OF THE INVENTION: Whether in the microelectronics industry or other industries that manufacture microstructures (such as micromachines, magnetoresistive write heads), there is a constant need to reduce feature size. In the microelectronics industry, the need is to reduce the size of the microelectronic device and/or to accommodate more circuitry in a given wafer size. However, in order to make smaller devices, it is necessary to make breakthroughs in lithography lithography to reliably distinguish features and gaps. The optical resolution is limited in part to the wavelength of light (or other radiation) used to make the lithographic pattern. Therefore, the use of short-wavelength light has become a trend in lithography processes. Recent developments have shifted from I-line radiation with a wavelength of 3 50 nm to radiation with a wavelength of 248 nm. For the need for smaller size in the future, it is necessary to shorten the wavelength used to l$3 nm. Unfortunately, the photoresist composition used in the lithography process for wavelengths of 24 8 nm is unstable under such short wavelengths. The photoresist composition must not only have suitable optical properties to provide a suitable image resolution at the desired wavelength of light, but the composition still needs to have suitable chemical and mechanical properties to enable the image to be imaged from the light. The transfer is transferred to the substrate layer underlying it. Therefore, a positive photoresist having selective exposure characteristics to the pattern must have suitable dissolution reaction characteristics (e.g., selective dissolution in the exposed region) to obtain a desired photoresist structure. Despite the extensive experience of phase I in the use of aqueous alkaline developer solutions in lithography, the reaction in the developer solution is still critical to determining proper dissolution. Page 4 This paper scale applies to China National Standard (CNS) A4 specification (210Χ 297 mm) (Please read the note on the back and then this page) 1·.·· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 1301928 A7 B7 V. INSTRUCTIONS () The patterned photoresist structure (after development) must have sufficient resistance to the foot - to transfer the pattern to the underlying substrate layer. Typically, pattern transfer is achieved via wet chemical etching or ion etching. Whether the patterned photoresist layer can withstand the pattern transfer etch process (i.e., whether the photoresist layer is sufficiently resistant during etching) is a very important feature of the photoresist composition. When certain photoresist compositions are designed for radiation with a wavelength of 1 93 nm, these compositions tend to exhibit better performance in the above-mentioned fields and do not exhibit better imaging at shorter wavelengths. The advantage of resolution. Although the photoresist composition disclosed in the above reference has progressed over the prior art, lithography can be applied to a photoresist composition for lithography at a wavelength of 193 nm at a wavelength of 193 nm. Still need improvement. For example, photoresist compositions are still expected to have better development characteristics (e.g., resolution, development speed, contrast, shrinkage, etc.), better etch resistance, and better lithography process range. Especially in the shrinkage property, the photoresist composition is expected to be further improved. SUMMARY OF THE INVENTION: Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative Printed The present invention relates to a photoresist composition having high resolution for lithography, and (a) less exposed during exposure and/or post-exposure baking. Shrinkage; (b) preferred dissolution characteristics; and/or (c) preferred formulation/filming properties. Moreover, the compositions of the present invention have better imaging results when imaged at 93 nm imaging radiation (or possibly at other wavelengths of radiation). The present invention also provides the use of the photoresist composition of the present invention to create a photoresist junction. The fifth paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301928 a7 __ B7 V. Invention Description () lithography a method; and a method of transferring a pattern to a covered-covered substrate layer in such a photoresist structure. The lithography method of the present invention has better characteristics when selectively irradiating a pattern with ultraviolet light having a wavelength of 193 nm. Preferably, the method of the present invention is capable of resolving features having a size of less than 150 nm, especially less than 130 nm in size and without the use of phase shift mask features. One aspect of the invention is a photoresist composition comprising: (a) an imaging polymer, and (b) a pair of light-sensitive acid generators comprising at least monomer units, the single The bulk unit has a side group (hereinafter referred to as "PALM" group) which contains a polybasic acid unstable epitope which protrudes from the polymerizable portion of the monomer. The PALM group may extend from the cyclic hydrocarbon monomer or from other suitable monomer units that form the imaging polymer backbone. Preferred PALM groups are those having a larger volume of terminal groups, such as an alicyclic group and/or a hydrocarbon having a medium length carbon chain (i.e., CpCm). The preferred PALM group inhibits the dissolution of the photoresist composition in an alkaline aqueous solution in the absence of an acid produced by the acid generator. Preferably, the imaging polymer comprises (i) a cyclic olefinic monomer unit (i.e., a polymerizable moiety in the monomer unit constituting the polymer) in the polymer backbone; and/or (ii) A larger volume of alicyclic epitope at the end of the PALM. group. In the absence of an acid produced by an acid generator, the image forming polymer is preferably substantially insoluble in an aqueous alkaline solution, and the photoresist is referred to as a positive photoresist. Other aspects of the present invention are PALM-containing monomers and the Chinese National Standard (CNS) A4 specification (210X297 mm) applicable to the 6th page of the paper. (Please read the back note first and then 9 pages)本1····································································································· A method of creating a patterned photoresist structure, the method comprising: (a) providing a substrate having a surface layer of a photoresist composition of the invention, and (b) patterning the light with imaging radiation a resist layer that exposes a portion of the photonic layer to the imaged radiation; and (〇) contacting the photoresist layer with an aqueous solution of the inspecting developer to remove the exposed portion of the photoresist layer to create a pattern Preferably, in step (b) of the above method, ultraviolet light having a wavelength of 193 nm is used. The present invention also contemplates the use of a patterned photoresist structure containing the composition of the present invention to produce conductive Sexual, semi-conductive Processes of Magnetic or Insulating Structures These and other aspects of the present invention will be described in detail below. Detailed Description of the Invention: Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed The photoresist composition of the present invention is generally characterized by having an internal PALM side An imaging polymer of monomer units of a group. These compositions are preferably capable of providing a high resolution lithography pattern at 193 nm light and have the following characteristics: (a) during exposure and/or post exposure baking Small shrinkage phenomenon; (b) preferred dissolution characteristics; and/or (c) preferred formulation/film uniformity. The present invention further encompasses a patterned photoresist structure containing the photoresist composition of the present invention, A method of creating the photoresist structure; and using the photoresist structure to form a conductive top paper scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301928 A7 B7 5. Invention Description () Sexual, semi-conductive And/or process for insulating structures. The present invention also encompasses polymerizable monomers having a -PALM side group. The photoresist composition of the present invention generally comprises at least (a) an image forming polymer; and (b) a light sensitive acid. Produce Polymer comprises at least a monomer unit having a pendant group of preferred PALM contents PALM side group of the monomer unit may be represented by the following formula:. -Μ- [ί] ρ C = 0 i ①

I x C=〇 i (請先閲讀背面之注意事項再本頁) 本一訂 Μ 經濟部智慧財產局員工消費合作社印製其中 (i) X為一可與每一鄰近羧基表位上的氧與/或内含多元酸不穩定表位本身形成至少一酸不穩定鍵之部分， (ii) Μ為一較佳之聚合骨幹表位，其係分別選自由一乙烯表位與環狀烯烴表位或其他合適的可聚合表位所組成之群組中， (iii) Ζ為一種表位，其係選自由環烷基、直鍊烷基第8頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐)I x C=〇i (please read the notes on the back and then this page) This is a copy of the Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative. (i) X is an oxygen that can be associated with each adjacent carboxyl group. And/or a portion of the polyacid-labile epitope itself that forms at least one acid labile bond, (ii) Μ is a preferred polymeric backbone epitope selected from an ethylene epitope and a cyclic olefin epitope, respectively. Or a group consisting of other suitable polymerizable epitopes, (iii) Ζ is an epitope selected from the group consisting of a cycloalkyl group, a linear alkyl group, and the paper is applicable to the Chinese National Standard (CNS) A4. Specifications (210X297 mm)

I 1301928 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（） (CrC3)、或其他空間上適的表位所組成之群組中； (iv) p係分別可為〇或1 ;及 (v) Q為一具較大體積的末端基團。成像聚合物亦可含有其他如下所述之單體單元，其係會因聚合的難易度而影響骨幹單元M、 '〜硬释。例如，若聚合物只包含其他含有環狀缔烴聚合表位之單體單元時，則Μ較佳係選自（a)含三氟甲基側基困表位之二:: 表位（此時P為〇，Μ較佳係可形成三氟軋τ基丙烯酸酯之一部份）；與（b)其他環狀婦烴單體單元。其士直平兀。右成像聚合物不含内含環狀烯烴聚合表位之單體單元，或若成像聚么物更包含可與環狀缔煙單體進行自由基聚合反應美國專利申請案09/566397號中所描述）之非環狀埽烴單體單元時’ Μ較佳係選自（〇—乙缔表位，其具有⑴ 一三氟甲基側基表位（Ρ為0，Μ較佳係可形成三氣甲基丙埽酸酯之一部份），（Π)—甲基側基表位化為^%較佳係可形成三氟甲基丙婦酸醋之一部份），或（iii)不含側基表位（非PALM基團-其中ρ為〇，μ較佳係可形成丙烯酸酯之一部份）；與（b )其他環狀埽烴單體單元。關於選取Μ的其他考量因素尚包含當認為較佳成像聚合物為（i)在聚合物骨幹中具有環狀烯烴單體單元（亦即，形成聚合物之單體中的可聚合部分）；（ii)PALM基團末端為具較大體積之脂環族表位之情況。因此，如果聚第9頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閱讀背面之注意事項再ί本頁) 本丨·.訂- -線， 1301928 五、發明説明（ σ物中’又有其他單體單元含有可與環狀烯烴聚合之表位且末响基團Q也不包含脂環族表位時，則μ較佳係為一環狀缔烴。 Φ，則&本發明中’只要能與成像聚合物中的其他單體相容，且甚4* Α I 座生的組成物可作為光阻劑，則成像聚合物中的Μ可由任何合適的可聚合表位中選取。以下為一些可能的Μ表位結構（II): (請先閲讀背面之注意事項再I 1301928 A7 B7 Ministry of Economic Affairs Intellectual Property Office Employees' Cooperatives Print 5, Inventions () (CrC3), or other groups of spatially appropriate epitopes; (iv) p-series may be 〇 or 1 And (v) Q is a larger volume of terminal groups. The image forming polymer may also contain other monomer units as described below, which may affect the backbone unit M, '~ hard release due to the ease of polymerization. For example, if the polymer contains only other monomeric units containing a cyclic hydrocarbon-polymerized epitope, then hydrazine is preferably selected from the group consisting of (a) a trifluoromethyl-containing pendant group:: epitope (this When P is 〇, Μ is preferably a part of a trifluoro-rolling τ-based acrylate; and (b) other cyclic sulfone monomer units. The taxi is straight and flat. The right imaging polymer is free of monomeric units containing a cyclic olefin polymerized epitope, or if the imaging polymer further comprises free radical polymerization with a cyclic Smoking monomer, US Patent Application Serial No. 09/566,397 In the case of the acyclic terpene hydrocarbon monomer unit, the oxime is preferably selected from the group consisting of (1) a trifluoromethyl side group epitope (Ρ is 0, and Μ is preferably formed). One part of trimethyl methacrylate, (Π)-methyl side group is expressed as ^%, preferably forms part of trifluoromethyl acetoacetate), or (iii There are no pendant group epitopes (non-PALM groups - where ρ is 〇, μ is preferred to form part of the acrylate); and (b) other cyclic oxime hydrocarbon monomer units. Other considerations regarding the selection of hydrazine include the inclusion of a preferred imaging polymer as (i) having a cyclic olefin monomer unit (i.e., a polymerizable moiety in the monomer forming the polymer) in the polymer backbone; Ii) The end of the PALM group is a alicyclic epitope with a larger volume. Therefore, if the page size of the 9th page is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and then the page). 丨·..--Line, 1301928 V. Invention It is to be noted that when another monomer unit contains an epitope which can be polymerized with a cyclic olefin and the terminal group Q does not contain an alicyclic epitope, μ is preferably a cyclic hydrocarbon. Φ, then & In the present invention, as long as it is compatible with other monomers in the image forming polymer, and a composition of 4* Α I is used as a photoresist, the ruthenium in the image forming polymer can be any suitable Selected from the polymerizable epitopes. The following are some possible Μ epitope structures (II): (Please read the notes on the back first.

Η I I•c——c- (Π) 本頁) Η v玎· 經濟部智慧財產局員工消費合作社印製其中位置1代表一與ζ間的鍵結，或一與羧基表直接鍵結，且Ri較佳係選自Η、CH3、或CF3中 X部分的結構可能會有所改變，只要（a)0-x 持其酸不穩定性，以致其在暴露於光敏感酸產生後所產生的酸時，該键結可能會斷裂；與/或（b)x 有酸不穩定鍵（羧基表位中之氧以外的鍵結）。較因為所選取X之特性，每一 0-X键結代表至少一定表位，其係選自由三級烷氧基（丁烷氧基更佳）、及縮趁所組成之群組中。該酸不穩定表位較佳係反應，因而產生更多的酸，且該成像聚合物鍊上第10頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐）位間的〇鍵仍保物照光本身含佳是，酸不穩縮酮、能與酸的殘餘 A7Η II•c——c- (Π) This page) Η v玎· Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative prints where position 1 represents a bond with the day, or a bond directly to the carboxyl table, and Preferably, the structure of Ri selected from the X moiety of ruthenium, CH3, or CF3 may be changed as long as (a) 0-x is acid unstable so that it is produced after exposure to light sensitive acid. In the case of an acid, the bond may be broken; and/or (b)x has an acid labile bond (bonding other than oxygen in the carboxyl epitope). Each 0-X bond represents at least a certain epitope, which is selected from the group consisting of a tertiary alkoxy group (better butoxy group), and a condensed group, because of the characteristics of X selected. The acid labile epitope is preferably a reaction, thereby producing more acid, and the 10th page of the imaged polymer chain is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm). Still protected by the light itself, the acid is unstable, the ketone, and the residue of the acid A7

1301928 — 五、發明説明（） P刀’與上有較大體積基團Q的殘餘部分，均可促進光· p且暴路於光照射下之部分於鹼中溶解。若有需要，所選取的X特性，可使酸不穩定表位在PALM基團之不同X-0 位置會有所不同。更佳的情況是，所選取的X，使Ho 代表兩個鍵結在一起的酸不穩定醋基團。一般來說，若匕.、了含有Q的分子外，任一反應副產物分子為低分子1或接受曝光的光阻體積不會在曝光時或後曝光烘烤時收縮太多時，所選取的X為較佳的X。因X部分具有兩個鍵結位置，所以X部分有較多的酸不穩定（或其他形式）鍵（例如，X為具有三個官能基的 J衣己坡）。其他可供選擇的X結構可能含有一核心表位 (例如’一環狀結構），其係具有一或多個三級烷基側基而酸不穩定鍵0_x係介於羧基表位中的氧與X部分中的三級烷基表位之間。因光阻係以1 93nm的光成係·’較佳是X部分並不會引入任何不飽和碳鍵至光阻中。末端基團Q較好是一具較大體積的基團。若含一或多個具較大體積的組成（例如飽和脂環族結構）將更佳。較佳是Q中不含不飽和碳-碳键。較佳的脂環族結構係選自由正-茨基（norbornyl)、金剛烷基與飽和稠環碳氫化合物（雙環結構較佳）所組成之群組中。或者，具較大體積的組成可能為一非環狀飽和碳氫化合物（直鍊或具有分枝）’以内含至少1 0個碳原子者為較佳。成像聚合物可能為上述含有PALM基團之單體的同第11頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再_本頁) 丨：訂·1301928 — V. DESCRIPTION OF THE INVENTION () The P-knife' and the remaining portion of the larger volume group Q can promote the dissolution of the light·p and the portion of the storm under the light irradiation in the alkali. If desired, the selected X characteristics will cause the acid labile epitope to differ at the different X-0 positions of the PALM group. More preferably, the selected X is such that Ho represents two acid labile vine groups bonded together. In general, if the molecule containing Q is in addition to the molecule containing Q, the molecular weight of any reaction by-product is low or the volume of the resist that is exposed to exposure does not shrink too much during exposure or post-exposure baking. X is the preferred X. Since the X moiety has two bonding positions, the X moiety has more acid labile (or other forms) bonds (for example, X is a J-slope with three functional groups). Other alternative X structures may contain a core epitope (eg, a 'cyclic structure') having one or more tertiary alkyl side groups and an acid labile bond 0_x being oxygen in the carboxyl epitope. Between the tertiary alkyl epitope in the X moiety. Since the photoresist is made of light of 193 nm, it is preferable that the X portion does not introduce any unsaturated carbon bond into the photoresist. The terminal group Q is preferably a relatively large volume group. It would be better if one or more compositions having a larger volume (e.g., a saturated alicyclic structure) were included. Preferably, Q contains no unsaturated carbon-carbon bonds. The preferred alicyclic structure is selected from the group consisting of norbornyl, adamantyl and saturated fused-ring hydrocarbons (better bicyclic structures). Alternatively, a composition having a larger volume may be an acyclic saturated hydrocarbon (straight or branched), preferably having at least 10 carbon atoms. The imaging polymer may be the same as the above-mentioned PALM-containing monomer and the 11th page of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the back note before this page) 丨: Booking·

經濟部智慧財產局員X消費合作社印製 1301928Ministry of Economic Affairs, Intellectual Property Officer X Consumer Cooperative Printed 1301928

五、發明説明( (請先閲讀背面之注意事項再^^本頁) 聚物，或者亦可包含除了該内含PALM基團之單體外的其他單體單元。例如成像聚合物可能含有一或多種下列單體：（a)内含酸不穩定表位（非pALM基團）的環狀烯烴單體，其係可抑制光阻在鹼性水溶液中溶解；内含極性表位的環狀埽烴單體，其係可促進光組在鹼性水ς 液中溶解；（〇含有如美國專利申請案〇9/566395號之内酯側基表位之環狀烯烴單體；（d)不屬於（a)_(c)的其他環狀晞烴單體單元，例如不含側基表位之單體單元、側基表位為不具極性與不具酸不穩定性等等；（e)如美國專利申請案09/566397號所述，可與含pALM基團之單髀進行自由基共聚反應的非環狀烯烴單體；（f)可與本 PALM基團之單體進行加成聚合反應之非環狀烯烴單體 (例如’丙烯酸酯單體）；與/或（g)其他可與光阻成分中之聚合物功能相容之單體。如上所述，在選擇含palm .基團單體中的M，與選擇成像聚合物中所含的其他單體時，較佳的狀況是使該成像聚合物含有環狀烯烴骨幹與/或使其至少一些側基團中具有脂環族表位。經濟部智慧財產局員工消費合作社印製環狀烯烴單元可為任一種至少含有酸不穩定表位且可抑制鹼性水溶液中所產生之溶解現象的環狀缔煙單體單元。這種環狀烯烴單體的例子可由下式（III)表示，其中R2代表一酸不穩定保護表位，且η為0或某些正整數 (較佳是0或1)。第頭本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 A7 B7 五、發明説明（5. Description of the invention ((Please read the precautions on the back and then the ^^ page) Polymer, or may also contain other monomer units than the monomer containing the PALM group. For example, the imaging polymer may contain one Or a plurality of the following monomers: (a) a cyclic olefin monomer containing an acid labile epitope (non-pALM group) which inhibits dissolution of the photoresist in an aqueous alkaline solution; a ring containing a polar epitope a terpene hydrocarbon monomer which promotes dissolution of the optical group in the alkaline aqueous mash; (〇 a cyclic olefin monomer containing a pendant lactide epitope of the U.S. Patent Application Serial No. 9/566,395; (d) Other cyclic terpene hydrocarbon monomer units not belonging to (a)-(c), such as monomer units without pendant group epitopes, side group epitopes are non-polar and non-acid-inert, etc.; An acyclic olefin monomer which can be subjected to radical copolymerization with a mono-palladium group containing a pALM group as described in U.S. Patent Application Serial No. 09/566,397; (f) Addition polymerization with a monomer of the PALM group Reaction of the non-cyclic olefin monomer (such as 'acrylate monomer'; and / or (g) other polymer work with the photoresist component Compatible monomers. As described above, in selecting M in the palm group-containing monomer, and selecting other monomers contained in the image forming polymer, it is preferred that the image forming polymer contains a ring. The olefinic backbone and/or has at least some of its side groups having an alicyclic epitope. The Ministry of Economic Intelligence, the Intellectual Property Bureau, the employee consumption cooperative, the printed cyclic olefin unit may be any one containing at least an acid labile epitope and inhibiting alkali A cyclic smoking monomer unit which is soluble in the aqueous solution. An example of such a cyclic olefin monomer can be represented by the following formula (III), wherein R 2 represents an acid labile protective epitope, and η is 0 or Some positive integers (preferably 0 or 1). The first paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301928 A7 B7 V. Description of the invention (

η ⑽ 更佳是，該環狀烯烴單元（a)係選自下列More preferably, the cyclic olefin unit (a) is selected from the following

r2 b) 0 (IV) (請先閲讀背面之注意事項再填寫本頁) 本一 r2R2 b) 0 (IV) (Please read the notes on the back and fill out this page) This one r2

-U 經濟部智慧財產局員工消費合作社印製其中r2代表一酸不穩定保護表位。較佳的酸不穩定保護表位係選自由羧酸三級烷基（或環烷基）酯（例如三級丁基、甲基環戊基、甲基環己基、甲基金剛烷基）、縮酮酯、及縮醛酯所組成之群組中。羧酸三級丁基酯與甲基環己基為上述表位中最佳的酸不穩定保護表位。若需要，使用時可組合具不同保護官能基之環狀婦烴單元（a)。環烯烴單元（b)可能為任一種具極性官能基團且可促進鹼性水溶液中溶解度之環狀烯烴單體單元。環狀婦烴單體單元之例子包含下列以式（V)表示之單體，其中R3 第13頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 A7 B7 五、發明説明（）代表一酸性極性表位，n為〇或某些正整數（0或丨較佳）-U Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in which r2 represents an acid-labile protective epitope. Preferred acid labile protective epitopes are selected from the group consisting of tertiary alkyl (or cycloalkyl) carboxylic acid esters (eg, tertiary butyl, methylcyclopentyl, methylcyclohexyl, methyladamantyl), A group consisting of a ketal ester, and an acetal ester. The tertiary butyl carboxylate and methylcyclohexyl group are the best acid labile protection epitopes of the above epitopes. If desired, a cyclic hydrocarbon unit (a) having different protective functional groups can be combined for use. The cycloolefin unit (b) may be any cyclic olefin monomer unit having a polar functional group and which promotes solubility in an aqueous alkaline solution. Examples of the cyclic hydrocarbon monomer unit include the following monomers represented by the formula (V), wherein the R3 page 13 paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301928 A7 B7 V. Description of the invention () represents an acidic polar epitope, n is 〇 or some positive integer (0 or better)

(V) η 較佳的環狀婦烴單元（b)可選自下列(V) η Preferred cyclic hydrocarbon unit (b) may be selected from the following

b) "Ο (VI) (請先閲讀背面之注意事項再本頁) 本 ,訂· 其係經濟部智慧財產局員工消費合作社印製其中代表一極性表位（較佳為一酸性極性表位）可促進鹼性水溶液中之溶解度。較佳的酸性極性表位之 pKa約為1 3或更低。較佳的酸性極性表位係含有極性基團，該極性基團選自由羧基、磺醯胺基、氟醇與其他酸性極性基團所組成之群組中。較佳的酸性極性表位為羧基。若需要，可組合具不同酸性極性官能基之環烯烴單元（b)來使用。環狀埽烴單體單元（d)較佳是具有下列結構：第14頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 A7 B7 五、發明説明（b) "Ο (VI) (Please read the note on the back and then this page) This book is printed by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperative, which represents a polar epitope (preferably an acidic polarity table). Bit) promotes solubility in an aqueous alkaline solution. Preferred acidic polar epitopes have a pKa of about 13 or less. Preferred acidic polar epitopes contain a polar group selected from the group consisting of a carboxyl group, a sulfonamide group, a fluoroalcohol and other acidic polar groups. A preferred acidic polar epitope is a carboxy group. If necessary, a cyclic olefin unit (b) having different acidic polar functional groups may be used in combination. The cyclic terpene hydrocarbon monomer unit (d) preferably has the following structure: Page 14 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301928 A7 B7 V. Description of the invention (

(VII) η 其中η為0或一整數，R4係選自由氫、烷基與一磺醯胺基所組成之群組中。更佳是，單體單元（d)係選自下列結構式： (請先閲讀背面之注意事項再峡讀本頁) 本一 •>\呑(VII) η wherein η is 0 or an integer, and R4 is selected from the group consisting of hydrogen, an alkyl group and a monosulfonylamino group. More preferably, the monomer unit (d) is selected from the following structural formula: (Please read the notes on the back and read the page again) This one •>\呑

r4 b) r4 (vm) -線·:· 經濟部智慧財產局員工消費合作社印製其中R4係選自由氫、及Ci-Cs烷基所組成之群組中。若需要，可組合環烯烴單元（d)來使用。較佳的環烯烴單元 (d)為R4是C3-C5烷基，更佳是，R4是C4烷基。一般來說，本發明中較佳的成像聚合物應用於製造積體電路結構與其他微結構之微影製程時，該成像聚合物至少包含約 10%(莫耳百分比）之含 PALM之單體單第15頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) A7 B7 1301928 五、發明説明（）元’更佳是含有1〇-5〇%(莫耳百分比）之含pALM之單體單元，最佳是含20-40%(莫耳百分比）之含pALM之單體單元。除此之外，成像聚合物中的其他組成量，較佳是當聚合物以193 nm的光進行成像輻射時，那些可作為光阻配方者（亦即’在這些聚合物中’以含paLM基困之單體單元’代替部分含酸不穩定表位之單髏單元）。因此，舉例來說’在本處參考文獻之美國專利第5 843 624號第6，124,074號、第6’；177,228號中所揭露的聚合物，與美國專利申請案09/566,395與〇9/566,397中含有酸不稃定表位的特定單體單元，至少一部分可以被含pALM^ 單體取代。本發明並不限於將含PALM之單體單元用於任一特定聚合物或指定的光阻配方中。除了成像聚合物，本發明之光阻組成物含有對輕射R4 b) r4 (vm) - line ·: · Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, where R4 is selected from the group consisting of hydrogen and Ci-Cs alkyl. If necessary, the cycloolefin unit (d) can be used in combination. The preferred cycloolefin unit (d) is that R4 is a C3-C5 alkyl group, and more preferably, R4 is a C4 alkyl group. In general, when the preferred imaging polymer of the present invention is used in a lithography process for making integrated circuit structures and other microstructures, the image forming polymer comprises at least about 10% (% by mole) of PALM-containing monomers. Page 15 of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 1301928 V. Invention description () Yuan' is better with p〇M containing 1〇-5〇% (% of mole) The monomer unit is preferably a monomer unit containing pALM in an amount of 20-40% by mole. In addition, other components in the imaging polymer, preferably when the polymer is imaged with 193 nm light, those that act as photoresist formulations (ie, 'in these polymers' contain paLM The monomer unit of the base is replaced by a single unit containing an acid labile epitope. Thus, for example, the polymers disclosed in U.S. Patent No. 5,843,624, the disclosure of which is hereby incorporated herein by reference in its entirety in its entirety in U.S. 566,397 contains a particular monomeric unit of an acid-unstable epitope, at least a portion of which may be substituted with a pALM^-containing monomer. The invention is not limited to the use of PALM-containing monomer units in any particular polymer or specified photoresist formulation. In addition to the imaging polymer, the photoresist composition of the present invention contains a pair of light shots

敏感（光敏感）之酸產生物。本發明不限於使用任—A 、 —待定的酸產生物或酸產生物之組合，所以本發明之優點之為可使用前技中各種已知的酸產生物。較佳的酸產生物為含有較少量（較佳係不含）的芳香族表位。當使用内& 芳香基之酸產生物時，酸產生物於193nm波長下的吸特性可能會限制配方中可被誘發之酸產生物的量。經濟部智慧財產局員工消費合作社印製合適的酸產生物實例包括（但較佳的選擇仍為以卢基來取代一或多個任一指定之芳香族表位）諸如三芳香基硫#六氟焦銻酸鹽、雙芳香基碘鏞六氟焦鋒酸睡之續的鐳鹽，六氟化砷，triflate，全氟烷基磺酸鹽（例如全氟甲烷磺酸鹽、全氟丁烷、全氟己烷磺酸鹽、全氣辛垸續酸鹽等）’諸如焦倍紛（例如，焦倍紛鹽中的= * 第16頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 1301928 A7 B7 五、發明説明（）酸鹽或焦倍酚鹽中的三（磺酸鹽））之類的具芳香取代基之磺酸鹽，羥基醯亞胺酯中的磺酸酯，磺醯氧基蓁二甲醯亞胺（N-樟腦續酿氧基蕃二甲酿亞胺、N -五氟苯基續醯氧基蓁二甲醯亞胺），α — 雙-磺醯基偶氮甲烷，蕃醌-4-疊氮，烷基雙戚及其他^ 本發明光阻組成物較佳更包含一體積較大之疏水性添加物（bulky，hydrophobic additives，「ΒΗ」添加物），此種物質在193nm下幾乎為透明的。「bh」添加物在傳統鹼性顯影劑水溶液下，可解析出超微之微影特徵和/ 或提昇其解析效果。「B Η」添加物較佳係含有至少_ 脂族表位。較佳是，該「ΒΗ」添加物含有至少1 〇個浐原子，更佳是含有至少1 4個碳原子，最佳是含有約以至6 0個碳原子，較佳的「Β η」添加物含有一個戈以之額外表位例如側酸不穩定基團，可於酸存在睡裂現象，故可用來作為促進暴露於輻射中之光阻於岭溶液中溶解度之成分。該「ΒΗ」添加物較佳係含有〜多個諸如酸不穩定側·基之其他表位，該酸不穩定側其酸存在下會裂解，以提供一可促進曝光後光組於驗1七液中溶解的組成部分。該「Β Η」：添加物較佳係係選自飽和膽固醇類化合物、非膽固醇類之環脂族化合物在至少兩個脂環族表位間含多元酸不穩定連結基團之# 膽固醇類的多環脂族化合物所組成之族群φ。 # 吏隹白勺「ΒΗ」添加物包括諸如三級丁基-3 -三氟乙醯石膽酸匕之類的石膽酸酯、金剛烷基甲酸三級丁自旨及譬_ Α 曰人叉-隻剛坡基甲酸三級丁酯。雙-金剛烷基甲酸三級丁酿為最彳圭、第17頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再本ΪSensitive (light sensitive) acid generator. The present invention is not limited to the use of any of -A, -detailed acid generators or combinations of acid generators, so it is an advantage of the present invention that various known acid generators of the prior art can be used. Preferred acid generators are those which contain a minor amount, preferably not containing, of an aromatic epitope. When an internal & aryl acid generator is used, the absorption characteristics of the acid generator at a wavelength of 193 nm may limit the amount of acid generator that can be induced in the formulation. Examples of suitable acid generators printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs include (but the preferred option is to replace one or more of the specified aromatic epitopes with lupin) such as triarylsulfur #六Fluorated pyrophosphate, diaryl iodonium hexafluoropyrofoam, a radium salt, arsenic hexafluoride, triflate, perfluoroalkyl sulfonate (eg perfluoromethanesulfonate, perfluorobutane) , perfluorohexane sulfonate, total gas octyl citrate, etc.) such as 焦倍 (for example, in the 焦倍盐盐 = * page 16 of this paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 public PCT) 1301928 A7 B7 V. Description of the invention () A sulfonate having an aromatic substituent such as a tris(sulfonate) in an acid salt or a pyrophenolate), a sulfonate in a hydroxy sulfoximine, Sulfomethoxy 蓁 dimethyl quinone imine (N-camphor continuation of oxydienol, N-pentafluorophenyl hydrazine oxime imine), α-bis-sulfonyl Azomethane, anthracene-4-azide, alkyl biguanide and others. The photoresist composition of the present invention preferably further comprises a bulky hydrophobic additive. (bulky, hydrophobic alternative, "ΒΗ" additive), this substance is almost transparent at 193 nm. The "bh" additive can resolve ultra-fine lithographic features and/or enhance its analytical effect under a conventional aqueous alkaline developer solution. Preferably, the "B" additive contains at least a _ aliphatic epitope. Preferably, the "ΒΗ" additive contains at least one ruthenium atom, more preferably at least 14 carbon atoms, most preferably from about 60 carbon atoms, preferably a "Βη" additive. It contains an extra-epitope such as a side acid labile group, which can be cracked in acid, so it can be used as a component to promote the solubility of the photo-resistance in the radish solution. Preferably, the "ΒΗ" additive contains ~ more than one other epitope such as an acid labile side group, and the acid unstable side will be cleaved in the presence of an acid to provide a light group capable of promoting exposure after the test. The dissolved component of the liquid. The "Β": the additive is preferably selected from the group consisting of saturated cholesterol compounds, non-cholesterol cycloaliphatic compounds containing at least two alicyclic epitopes containing polybasic acid labile linking groups of #cholesterol A group φ composed of polycyclic aliphatic compounds. #吏隹"""""""""""""""""""""""""""""""""""""""" Fork-only ternary butyl succinate. The bis-adamantic acid tri-butyl is the most popular, page 17 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and then Ϊ

訂· 經濟部智慧財產局員工消費合作社印製 1301928 A7 B7 五、發明説明（）「BH」添加物，若有需要可組合不同「BH」添加物使用。- 本發明光阻組成物，在使用於標的基材之前，原則上 ό有/4副。溶劑可為任一種傳統上與酸催化光阻劑一起使用且不θ對組成成分效能產生.相反效果之溶劑。較佳的落劑為丙二醇單甲基醚醋酸酯、環己酮與乙基乙二酸單甲酸g旨。本發明之組成物可能更包含其他微量之輔助成分，例如前技中已知之染料/感光劑、鹼性添加物。較佳的鹼性添加物為可清除微量酸，並對光阻效能沒有負面影響之弱驗。較佳的驗添加物為（脂肪族或脂環族）三級烷胺或氫氧化二級燒铵，例如氫氧化三級·丁铵（T B A Η)。本發明光阻組成物較佳係含有佔組成物中全部成像聚合物重量百分比0·5·20%(更佳是3_丨5%)之酸產生物。當計入落劑時，總組成物中較佳係含重量百分比約為 5 0-90%义溶劑。組成物較佳係含重量百分比約佔全部成像聚合物1%或更低之前述鹼添加物。本發明光阻組成物較佳係含有至少佔組成物中全部成像聚合物重量百分比约5%的「ΒΗ」添加物，更佳是約1〇_25%的「βη」添加物’最佳是約10-20%的「ΒΗ」添加物。本發明含PALM之單體與其他單體可藉由已之技術進行合成。例如’當Μ為乙埽表位時，下列含PALM之單體結構（IX)可以經由實施例1之合成機制合成。第18頁 (請先閲讀背面之注意事項再本頁) .¾. 本一 •訂- 經濟部智慧財產局員工消費合作社印製Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1301928 A7 B7 V. Invention Description () "BH" additives, if necessary, can be combined with different "BH" additives. - In principle, the photoresist composition of the present invention has /4 pairs before being used in the target substrate. The solvent can be any solvent that has traditionally been used with acid catalyzed photoresists and which does not have the opposite effect on the potency of the constituents. Preferred binders are propylene glycol monomethyl ether acetate, cyclohexanone and ethyl oxalic acid monocarboxylic acid g. The composition of the present invention may further comprise other minor amounts of auxiliary ingredients such as dyes/sensitizers and alkaline additives known in the prior art. The preferred alkali additive is a weak test that removes traces of acid and does not adversely affect photoresist performance. Preferred additives are (aliphatic or alicyclic) tertiary alkylamines or secondary ammonium hydroxides such as tertiary butylammonium hydroxide (T B A oxime). The photoresist composition of the present invention preferably contains an acid generator in an amount of 0.5 to 20% by weight (more preferably 3 to 5%) based on the total weight of the image forming polymer in the composition. When the agent is included, the total composition preferably contains from about 50% to about 90% by weight of the solvent. Preferably, the composition contains the aforementioned base additive in an amount of about 1% by weight or less based on the total of the imaging polymer. Preferably, the photoresist composition of the present invention contains at least about 5% by weight of the total imaging polymer in the composition of the "ΒΗ" additive, more preferably about 1% to 25% of the "βη" additive. About 10-20% of the "ΒΗ" additive. The PALM-containing monomer of the present invention and other monomers can be synthesized by the prior art. For example, when the oxime is an acetamidine epitope, the following PALM-containing monomer structure (IX) can be synthesized via the synthesis mechanism of Example 1. Page 18 (Please read the notes on the back and then on this page) .3⁄4. Ben 1 - Printed by the Intellectual Property Office of the Ministry of Economic Affairs

本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) ^^—J A7 B7 1301928 五、發明説明（）This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ^^—J A7 B7 1301928 V. Description of invention ()

OX) 其中含PALM之聚合物骨幹係由乙烯烴構成，實施例2 例示了利用自由基聚合反應進行聚合之實施例。本發明並不限於任一特定成像聚合物之合成方法。成像聚合物較佳的合成方式為加成聚合或自由基聚合反應。其他適用於環狀烯烴聚合物與其他聚合物的技藝包括於美國專利第5,468,8 1 9號、第5,705,503號、第 5，843,624號與第6，048,664號號中所揭露之技藝。本發明中之較佳成像聚合物之平均分子量約為5,0〇〇- 100,000’以10,000-50,000為較佳，當本發明以含palm 之單體描述時’事實上本發明尚包含在聚合反應後才於聚合物上形成PALM基團之成像聚合物。經濟部智慧財產局員工消費合作社印製本發明光阻組成物可以以結合成像聚合物、酸產生物、選擇性的「BH」添加物與任何其他需要之成分以傳統方法製備。微影製程中使用之光阻組成物一般都含有相當量的溶劑。第19頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301928 A7 B7 五、發明説明（）本發明光阻組成物在以半導體基材製造積體電路為目的之微影製程中特別有用。尤其在波長193 nm之紫外光下進行之微影製程。當必須使用其他種光（中紫外光 248 nm、深紫外光、x光或電子束）時，本發明中之成分可以加入染料或感光劑加以調整（若有必要）。以下敘述為關於應用光阻組成物於製造半導體中的微影製程時之一般用法。半導體微影製程通常包括將圖形轉移到半導體基材上的一層材料。此一層材料可能為金屬導電層、陶瓷絕緣層、半導體層或其他材料，視終產品對材料的需求或位於製造過程中哪一過程而定。在許多例子中，抗反射層（Anti-reflective coating，ARC)會於覆蓋光阻層前覆蓋於材料層上。ARC層可為任何傳統ARC只要與酸催化光阻相容即可。原則上含有溶劑之光阻組成物係使用旋塗（spin coating)或其他技藝將其施用於目標半導體基材上。之後’覆有該光阻之基材被加熱（曝光前預烤）以移除溶劑並增加光阻層的内聚性。所施加覆蓋層厚度較佳為盡量與provisos相似，且非常均勻，並足以抵抗後續製程（一般為反應性離子蝕刻），以將微影圖形轉移到被覆蓋之基材材料層。較佳的曝光前預烤階段需時1 〇秒到1 5分鐘，以1 5秒到1分鐘為最佳。較佳的曝光前預烤階段溫度至少比玻璃轉化溫度低攝氏2 0度。將溶劑移除後，光阻層繼續以適當波長（例如波長為第20頁本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) (請先閲讀背面之注意事項再本頁) 訂· 經濟部智慧財產局員工消費合作社印製 1301928 A7 B7 五、發明説明（） 193nm的紫外光）照射，以進行對圖形具選撂 $谭性的曝光階段。此階段是以掃瞄粒子光束，例如電子走，这婦瞒基材，並選擇性的使光束能打到適當的圖形位w ^ 直上。一般來說，以例如1 9 3 nm的紫外光作波狀輻射昭如。土 “、、對時，選擇性的圖形曝光是經由置放於光阻層上的光罩造士 +邃成。以波長為1 93nm的紫外光來說，較佳的總曝光能量控制在工毫焦耳/平方公分或更低，較佳的範圍是50毫焦耳/平方公分或更低(例如15-30毫焦耳/平方公分）。進行選擇性圖形曝光後’光阻層會繼續進行洪烤以進一步完成酸催化反應，並提高曝光圖形的對比。較佳的曝光後烘烤步驟是於攝氏1 00- 1 75度下進行，更佳的溫度是攝氏1 25-1 60度。較佳曝光後烘烤睁間為3〇秒到 5分鐘。曝光後烘烤後’將光阻層與驗性溶液接觸，驗性溶液會選擇性的溶解受到曝光的光阻層，而得到所需要圖案化之光阻結構。較佳的鹼性溶液（顯影劑）為氫氧化四甲銨，本發明中較佳的光阻組成物可以傳統〇 . 2 6 N鹼性水溶液加以顯影，或也可以〇 · 1 4N或0.2 1 N或其他濃度鹼性水溶液加以顯影。基材上之最終光阻結構需加以乾燥，以移除剩餘之顯影溶劑。本發明光阻組成物之一般特性為所產生的光阻結構具有高抗蝕刻的性質。在一些實施例中，可以利用先前技術中的後矽化反應技術進一步增強光阻結構之抗蝕刻性。本發明中的組成可以使微影特徵具有再現性。第21頁本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐)OX) The polymer backbone containing PALM is composed of ethylene hydrocarbon, and Example 2 exemplifies an example of polymerization by radical polymerization. The invention is not limited to the synthesis of any particular imaging polymer. A preferred synthesis of the imaging polymer is an addition polymerization or a free radical polymerization reaction. Other techniques suitable for use in cyclic olefin polymers and other polymers are disclosed in U.S. Patent Nos. 5,468,8,9, 5,705,503, 5,843,624, and 6,048,664. Preferred imaging polymers of the present invention have an average molecular weight of from about 5,0 Å to about 100,000 Å, preferably from 10,000 to 50,000. When the invention is described as a palm-containing monomer, the invention is in fact included in the polymerization. The imaged polymer of the PALM group is formed on the polymer after the reaction. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives The photoresist composition of the present invention can be prepared in a conventional manner by combining an imaging polymer, an acid generator, a selective "BH" additive, and any other desired ingredients. The photoresist composition used in the lithography process generally contains a significant amount of solvent. Page 19 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301928 A7 B7 V. Inventive Note () The photoresist composition of the present invention is used in a lithography process for manufacturing integrated circuits on a semiconductor substrate. Especially useful. Especially in the lithography process under ultraviolet light with a wavelength of 193 nm. When other kinds of light (medium ultraviolet light 248 nm, deep ultraviolet light, x-ray or electron beam) must be used, the components of the present invention may be adjusted by adding a dye or a sensitizer if necessary. The following is a general description of the application of the photoresist composition to the lithography process in the fabrication of semiconductors. Semiconductor lithography processes typically involve the transfer of a pattern to a layer of material on a semiconductor substrate. This layer of material may be a metallic conductive layer, a ceramic insulating layer, a semiconducting layer or other material depending on the material requirements of the final product or which process is in the manufacturing process. In many instances, an anti-reflective coating (ARC) will cover the layer of material before covering the photoresist layer. The ARC layer can be any conventional ARC as long as it is compatible with acid catalyzed photoresist. The photoresist composition containing the solvent in principle is applied to the target semiconductor substrate using spin coating or other techniques. Thereafter, the substrate covered with the photoresist is heated (pre-baked before exposure) to remove the solvent and increase the cohesiveness of the photoresist layer. The thickness of the applied cover layer is preferably as similar as possible to provisos and is very uniform and sufficient to resist subsequent processes (typically reactive ion etching) to transfer the lithographic pattern to the layer of substrate material being covered. The preferred pre-exposure pre-bake phase takes from 1 to 15 minutes, preferably from 15 seconds to 1 minute. Preferably, the pre-exposure pre-bake stage temperature is at least 20 degrees Celsius lower than the glass transition temperature. After removing the solvent, the photoresist layer continues to be at the appropriate wavelength (for example, the wavelength is the 20th page of this paper scale applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm) (please read the back note before this page) · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1301928 A7 B7 V. Invention description () 193nm ultraviolet light) irradiation, in order to carry out the exposure stage of the graphic selection. This stage is to scan the particle beam, such as electrons, on the substrate, and selectively enable the beam to hit the appropriate pattern bit w^ straight. In general, ultraviolet light such as 193 nm is used as the undulating radiation. The selective pattern exposure of the soil ", when, is based on the mask produced on the photoresist layer + 邃。. With the wavelength of 93 nm ultraviolet light, the preferred total exposure energy control Millijoules per square centimeter or less, preferably in the range of 50 millijoules per square centimeter or less (eg, 15-30 millijoules per square centimeter). After selective pattern exposure, the photoresist layer will continue to be baked. To further complete the acid catalyzed reaction and improve the contrast of the exposure pattern. The preferred post-exposure baking step is performed at 10,000-175 degrees Celsius, and the better temperature is 1 25-1 60 degrees Celsius. The post-baking time is 3 sec to 5 minutes. After the post-exposure baking, the photoresist layer is contacted with the test solution, and the test solution selectively dissolves the exposed photoresist layer to obtain the desired patterning. The photoresist structure. The preferred alkaline solution (developer) is tetramethylammonium hydroxide. The preferred photoresist composition of the present invention can be developed by a conventional aqueous solution of 〇 2 6 N or may be 〇· Development of 1 4N or 0.2 1 N or other aqueous alkaline solution. The final photoresist structure is dried to remove the remaining developing solvent. The general characteristics of the photoresist composition of the present invention are that the resulting photoresist structure has high etch resistance properties. In some embodiments, prior The post-deuteration reaction technique in the technology further enhances the etch resistance of the photoresist structure. The composition of the present invention can make the lithography feature reproducible. Page 21 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 public) PCT)

經濟部智慧財產局員工消費合作社印製 A7 B7 1301928 五、發明説明（）光阻結構上的圖形可以轉移到被覆蓋之基材材料-* (例如陶瓷、金屬或半導體）上。此步驟一般可以離子蝕刻或其他蝕刻技術達成’其中使用離子蝕刻時，光阻層的抗蚀刻能力特別重要。因此本發明中的組成物與最終製成之光阻結構可用來製造圖案化的材料層結構，例如金屬線路、接觸或通道孔 '絕緣部分（例如波狀溝或淺的獨立溝）。供電容使用之溝結構等等設計於積體電路裝置時會使用的部分。關於以上之製程（陶瓷、金屬或半導體）特徵一般包括提供一用來刻畫圖形之材料層或一基材段，藉由覆蓋一層光阻層於該材料層或該基材段上，對光阻層上的圖形加以選擇性曝光，將光阻層置於溶劑中使圖形顯影，對光阻層已刻畫圖形空間之下的材料層加以蝕刻，藉以形成具所需之已刻畫圖形之材料層或基材段，之後自基材上移除剩餘的光阻。在某些實施例中，硬光罩可用於光阻層之下方以幫助圖形轉移到覆蓋於其下的材料層或基材段的更深處。上述製程的實施例可參考在本文參考文獻之美國專利第4,855,017號、第5,362,663號、第 5,429,7 1 0 號、第 5,562,80 1 號、第 5,618,751 號、第 5,744,376 號、第 5，8 0 1，0 9 4 號、第 5，8 2 1，1 6 9 號所揭露的製程。其他圖形移轉製程可參閱 Wayne Moreau所著”Semiconductor Lithography, Principles, Practices, and Materials，，一書中第 1 2、1 3 章（Plenum Press, 1 988)。但本發明並不限於任一特定的微影技術或裝置結構。第22頁本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐) (請先閲讀背面之注意事項再β本頁) 麵本一 vv'Ty 經濟部智慧財產局員工消費合作社印製 1301928 一 A7 _ B7 五、發明説明（） f施例1 1成PALM-甲篡丙烯酸酯軍體ΓΙΧ) 含有43.3克（0.297莫耳）的2,5-二甲基_2,5_己二醇溶液置於600毫升的二氣曱烷中，於室溫下加入30·0克 (0.2 9 7莫耳）的三乙胺。將溶液冷卻到約攝氏1 0度’利用漏斗以五小時之時間，加入含有65克（0·327莫耳）的 1-金剛烷基甲碳醯氯之250毫升二氯甲烷溶液中，加完後，以迴流方式攪拌混合溶液1 小時，將溶液過濾，濾掉反應中形成之氫氯化三乙胺，濾出液以水（X400毫升）沖洗三次，並以無水硫酸鍰脫水後，以減壓濃縮方式進行濃縮。濃縮液之後以層析管柱（矽膠、己烷/二氯甲烷：1/1)，可分離出63.9克產物。產物以核磁共振光譜辨識為2-(1-金剛烷基羧氧基）-2,5 —二甲烷-5-己醇。含23.8克（0.228莫耳）以蒸餾得到之甲基丙婦醯氯之二氯甲烷500毫升，以漏斗逐滴加入含有63.9克（0.207 莫耳）2-(1-金剛烷基羧氧基）-2,5-二甲基-5-己醇與23.1 克（0.228莫耳）的三乙胺的5 〇0毫升二氯甲烷溶液中。加完後，先於室溫下攪拌1 5小時，再以迴流方式攪拌混合溶液24小時，將溶液過濾，濾掉反應中形成之氫氯化三乙胺，濾出液以水（X400毫升）沖洗三次，並以無水硫酸鎂脫水，並以減壓濃縮方式進行濃縮。濃縮液之後通過層析管柱（矽膠、己烷/醋酸乙酯：85/15)三次，可分離出 60克產物。產物為PALM-甲基丙醯酯單體（IX)。第23頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再本頁)Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives A7 B7 1301928 V. INSTRUCTIONS () The pattern on the photoresist structure can be transferred to the covered substrate material -* (for example ceramic, metal or semiconductor). This step can generally be achieved by ion etching or other etching techniques. The etching resistance of the photoresist layer is particularly important when ion etching is used. Thus, the compositions of the present invention and the resulting photoresist structures can be used to fabricate patterned material layer structures such as metal lines, contacts or via holes 'insulating portions (e.g., wavy trenches or shallow individual trenches). The groove structure used for the capacitor, etc., is designed to be used in the integrated circuit device. The above process (ceramic, metal or semiconductor) features generally include providing a layer of material or a substrate segment for patterning, by covering a layer of photoresist on the layer of material or the substrate, the photoresist The pattern on the layer is selectively exposed, the photoresist layer is placed in a solvent to develop the pattern, and the layer of material under the patterned space of the photoresist layer is etched to form a layer of material having the desired patterned pattern or The substrate segment, after which the remaining photoresist is removed from the substrate. In some embodiments, a hard mask can be used underneath the photoresist layer to aid in the transfer of the pattern to a deeper portion of the layer of material or substrate underlying it. Examples of the above-described processes can be found in U.S. Patent Nos. 4,855,017, 5,362,663, 5,429,7 1 0, 5,562,80 1 , 5,618,751, 5,744,376, 5, 8 0. Processes disclosed in 1,0 9 4, 5, 8 2 1, 1 6 9 . Other graphics transfer processes can be found in Wayne Moreau, "Semiconductor Lithography, Principles, Practices, and Materials," in Chapters 1, 2, and 3 (Plenum Press, 1 988). However, the invention is not limited to any particular The lithography technology or device structure. Page 22 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the back note before the β page) Face-to-face vv'Ty Ministry of Economics Intellectual Property Bureau employee consumption cooperative printed 1301928 A7 _ B7 V. Invention description () f Example 1 1 into PALM-methacrylate 军 military ΓΙΧ) Contains 43.3 g (0.297 mol) of 2,5-dimethyl The base 2,5-hexanediol solution was placed in 600 ml of dioxane, and 30. 0 g (0.29 m mol) of triethylamine was added at room temperature. The solution was cooled to about 10 ° C. Add a solution of 65 g (0·327 mol) of 1-adamantyl carbenium chloride in 250 ml of dichloromethane over a period of five hours. After the addition, stir the mixed solution by reflux. After 1 hour, the solution was filtered, and the triethylamine hydrochloride formed in the reaction was filtered off and filtered off. The solution was washed three times with water (X 400 ml), dehydrated with anhydrous barium sulfate, and concentrated under reduced pressure. The concentrate was then applied to a chromatography column (tand, hexane/dichloromethane: 1/1). 63.9 g of product was isolated. The product was identified by nuclear magnetic resonance spectroscopy as 2-(1-adamantylcarboxyoxy)-2,5-dimethane-5-hexanol. 23.8 g (0.228 mol) was obtained by distillation. Methyl propyl sulfonium chloride, 500 ml of dichloromethane, was added dropwise with a funnel containing 63.9 g (0.207 mol) of 2-(1-adamantylcarboxyoxy)-2,5-dimethyl-5-hexyl The alcohol was mixed with 23.1 g (0.228 mol) of triethylamine in 5 ml of dichloromethane. After the addition, the mixture was stirred at room temperature for 15 hours, and the mixed solution was stirred under reflux for 24 hours. Filtration, the triethylamine hydrochloride formed in the reaction was filtered off, the filtrate was washed three times with water (X 400 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Column (gelatin, hexane / ethyl acetate: 85 / 15) three times, can be separated 60 grams of product. The product is PALM-methyl propyl decyl ester single (IX). Page 23 Paper scale applicable to Chinese National Standard (CNS) A4 size (210X297 mm) (Please re-read the notes on the back of this page)

VT 經濟部智慧財產局員工消費合作社印製 1301928VT Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1301928

(請先閱讀背面之注意事項再#if本頁) -·訂.(Please read the notes on the back and then #if this page) -·Book.

經濟部智慧財產局員工消費合作社印製五、發明説明（）實施例2 合成聚合物 0.135克（0.00082 1莫耳）的2-2，偶氮二異氰丙嫁 (AIBN)加入含有5.7克（0.0156莫耳）的PALM T基两酿酯（PALM)、3.48克（0.0156莫耳）的甲基丙醯酸異茨酿 (IBM A)、與4.0克（〇·〇2 35莫耳）甲基丙烯醯酸a-丁内酯 (GBLMA)的7 5.5克THF中。反應混合物在氮氣中緩慢迴流並並進一步再迴流環境中攪拌42小時。聚合反應完成後，冷卻至室溫，移至1.2升甲醇中，使其產生沉澱，攪拌一小時後過濾。過濾所得之（PALM-IBMA-GBLMA) 聚合物在真空、攝氏5 0度的條件下隔夜烘乾。實施例3 微影評估為了微影實驗，含有PALM-IBMA-GBLMA共聚合物之光阻成分可利用下列材料加以製備，下列各材料百八比為重量百分比。丙二醇單甲基醚醋酸酯 87.6 PALM-IBMA-GBLMA 共聚物 12 二-三級丁基苯鐺全氟辛烷磺酸鹽 0.36 全氟丁基磺醯氧基雙環[2.2.1]-庚-5- 0.06 晞-2,3-二碳甲醯亞氨氫氧化四丁銨 0.024 第24頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） """""""------- 1301928 A7 B7 五、發明説明（）光阻成分是利用旋塗（30秒）方式覆蓋於矽晶圓之抗反射材料層上（AR 19, Shipley Company)。光阻層以攝氏 1 30度的條件於真空加熱盤上進行軟烘烤6〇秒以得到 0.4mm厚的薄膜。晶圓之後以193nm輻射加以曝光 (Nikon步進機，〇.6NA)。曝光所得到之圖形為具有不同尺寸，最小為0 · 1 mm之線與空間陣列。曝光過後的晶圓之後於真空加熱盤上以攝氏150度進行曝光後烘烤9〇秒。之後晶圓以0.2 6 3 N氫氧化四甲銨顯影液（攪煉法）加以顯影。之後形成之圖形以掃瞒式電子顯微鏡（SEm)加以檢查。1 5 Onm或以上之線/空間對可以達到具清楚輪廓的解析效果。在收縮實驗中，光阻成分為利用旋轉塗蓋（3〇秒）在塗於覆蓋於矽晶圓之抗反射材料層上（AR19，shipley Company)。光阻層以攝氏1 3 0度的條件於真空加熱盤上進行軟烘烤60秒以得到0.4mm厚的薄膜。之後晶圓以波長為1 93 nm之輻射在不同劑量下加以曝光（Nikon步進機，0.6NA)。曝光過後的晶圓之後於真空加熱盤上以攝氏150度進行曝光後烘烤（PEB)90秒。在不同劑量下的薄膜厚度以介電厚度測量儀加以測量。薄膜收縮則以曝光前與曝光後之厚度變化加以計.算。由薄膜收縮實驗證實具較大體積的去保護產物（1 -金剛烷基甲羧酸）在進行PEB之後，仍存於光阻薄膜中。第25頁本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再頁) V玎· 經濟部智慧財產局員工消費合作社印製Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description () Example 2 synthetic polymer 0.135 g (0.00082 1 mol) of 2-2, azo diisocyanide (AIBN) added containing 5.7 g ( 0.0156 mol) of PALM T-based two-flavored ester (PALM), 3.48 g (0.0156 mol) of methylpropionic acid isopropene (IBM A), and 4.0 g (〇·〇2 35 mol) methyl Propylene decanoate a-butyrolactone (GBLMA) in 7 5.5 g of THF. The reaction mixture was slowly refluxed under nitrogen and stirred for a further 42 hours under reflux. After completion of the polymerization, it was cooled to room temperature, transferred to 1.2 liters of methanol to cause precipitation, and stirred for one hour and then filtered. The filtered (PALM-IBMA-GBLMA) polymer was dried overnight under vacuum at 50 °C. Example 3 Microshadow Evaluation For lithography experiments, a photoresist component containing a PALM-IBMA-GBLMA copolymer was prepared using the following materials, and the following materials were in weight percent. Propylene glycol monomethyl ether acetate 87.6 PALM-IBMA-GBLMA copolymer 12 di-tertiary butyl benzoquinone perfluorooctane sulfonate 0.36 perfluorobutyl sulfonyloxybicyclo[2.2.1]-g-5 - 0.06 晞-2,3-Dicarbamidine Iminoammonium hydroxide 0.024 Page 24 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) """""""------- 1301928 A7 B7 V. INSTRUCTIONS () The photoresist component is coated on the anti-reflective material layer of the germanium wafer by spin coating (30 seconds) (AR 19, Shipley Company) . The photoresist layer was soft baked on a vacuum heating pan for 6 sec at a temperature of 1 30 ° C to obtain a film of 0.4 mm thick. The wafer was then exposed to radiation at 193 nm (Nikon stepper, 〇.6NA). The pattern obtained by exposure is a line and space array with different sizes and a minimum of 0 · 1 mm. The exposed wafer was then post-exposure baked at 150 degrees Celsius on a vacuum heating plate for 9 seconds. Thereafter, the wafer was developed with a 0.2 6 3 N tetramethylammonium hydroxide developing solution (stirring method). The resulting pattern was examined with a broom electron microscope (SEm). A line/space pair of 1 5 Onm or above can achieve a clear outline resolution. In the shrinkage test, the photoresist component was applied to the anti-reflective material layer (AR19, shipley Company) overlying the germanium wafer by spin coating (3 sec.). The photoresist layer was soft baked on a vacuum heating pan for 60 seconds at a temperature of 130 ° C to obtain a film of 0.4 mm thick. The wafer was then exposed to radiation at a wavelength of 93 nm (Nikon stepper, 0.6NA). The exposed wafer was post-exposure baked (PEB) on a vacuum heating plate at 150 degrees Celsius for 90 seconds. The film thickness at different doses was measured using a dielectric thickness gauge. The shrinkage of the film is calculated by the change in thickness before and after exposure. It was confirmed by film shrinkage experiments that a relatively large volume of the deprotected product (1-adamantylcarboxylic acid) remained in the photoresist film after PEB. Page 25 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back page again) V玎· Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

Claims

1301928 m 〇〇 ο 第 A8SS 舰月六、申請專利範圍 1.1301928 m 〇〇 ο A8SS Ships VI. Application for patents 1.

一種光阻組成物，其至少包含（a)—成像聚合物、與（b) 一對光敏感的酸產生物，其中前述之成像聚合物至少包含一單體單元，該單體單元係具有自單體中可‘聚合部分伸出之一内含多元酸不穩定表位之側基團（palm 基團），該内含PALM基團之單體單元至少包含一含有至少10個碳原子之具較大體積的末端基團，該末端基團係選自由環脂族表位及非環狀飽和碳氫.化合物所組成之群組中，其中該内含PALM單體單元具下列式之結構： Ζ·]I ρ c=〇〇I x C=〇 .閲讀背 δ 之注意事項再頁經濟部智慧財產局員工消費合作社印製 Q 其 ⑴ 中 X為一可與每一鄰近羧基表位上的氧與/或内含多元酸不穩走表位本身形成至少一酸不穩定鍵之部分； (ii) Μ為一聚合骨幹表位，其係分別選自由一乙烯第26頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 1301928 A8 B8 C8 D8 申請專利範圍物量表位與環狀烯烴表位所組成之群組中； (iii) Z為一種表位，其係選自由環烷基及直鏈烷基 (C 1 - C 3)所組成之群組中； · (iv) P為〇或1 ;且 * (v) Q為該具較大體積的末端基團；該酸產生物係鏽鹽（onium salt)、六氣珅酸鹽 (hexafluoroarsenates)、三氟甲烧續酸鹽（triflates)、全說燒基續酸鹽（perfluoroalkane sulfonates)、.經取代之芳香基磺酸鹽、羥基醯亞胺的磺酸酯、N-磺醯氧基萘二曱醯亞胺（N-sulfonyloxynaphthalimides)、 α — α ’雙-磺醯基重氮甲烷（α. — α，bis-sulfonyl diazomethane) 、.萘醌 - 4 - 疊氮 (naphthoquinone-4-diazide)或烷基雙砜；其中該組成物包含〇 _ 5 - 2 0 %重量百分比的該酸產生該重量百分比係基於該組成物中該成像聚合物之總重 .閲讀背面之注意事項參 # 經濟部智慧財產局員工消費合作社印製 2·如申請專利範圍第1項所述之光阻組成物，其中該成像聚合物包含⑴一環狀烯烴單體單元，其係位於前述聚合物骨幹中；與/或（ii) 一較大.·體積的脂環族表位，.其係位於前述PALM基團末端。 3 ·如申請專利範圍第1項所述之光阻組成物，其中該内第27頁本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐） 1301928 Α8 Β8 C8 D8 、申請專利範圍含palm聚合幹表位。物之單體單元至少包含一種環狀烯烴骨如申凊專利範圍第1項所述之光阻組成物，其中.該内 S PALM聚合物之單體單元至少包含一種乙烯骨幹表位。申吻專利範圍第4項所述之光阻組成物·，其中該内各PALM聚合物之單體單元至少包含一自前述乙烯骨幹表位伸出之曱基側基團或三氟曱基側基團，該曱基側基團或該三氟甲基側基團與該PALM基團並不同在一處。 .閲讀背 © 之注意項 4 i 經濟部智慧財產局員工消費合作社印製 6·如申請專利範圍第1項所述之光阻組成物，其中該成像聚合物更包含至少一種單元單體，該單元單體係選自由下列物質所組成之群組中··内含除PALM基團以外之可抑制光阻在鹼彳生水溶液中溶解之酸不穩定表位的環狀婦烴單體單元；（b)内含可修進光阻在鹼性水溶液中溶解之極性表位的環狀烯烴單體；（c)内含内酯側基表位之環狀烯烴單體；（d)不含側基表位之單體單元、或側基表位為不具極性與不具酸不穩定性之環狀稀L單體’（e)可與前述内含PALM基團之單體單元進行自由基反應的非環狀烯烴單體單元；及⑴可與前述内含PALM基團單體單元進行加成聚合反應之非環狀第2煩本紙中國&標準（CNS)巧格（21〇 χ 297公石A photoresist composition comprising at least (a) an image forming polymer, and (b) a pair of light sensitive acid generators, wherein said image forming polymer comprises at least one monomer unit, said monomer unit having a monomer group in which a polymerizable portion protrudes to contain a side group (palm group) of a polybasic acid unstable epitope, and the monomer unit containing the PALM group contains at least one having at least 10 carbon atoms. a larger volume of terminal groups selected from the group consisting of cycloaliphatic epitopes and acyclic saturated hydrocarbons, wherein the internal PALM monomer unit has the structure of the formula: Ζ·]I ρ c=〇〇I x C=〇.Notes on reading back δ. Reprinted from Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed Q, (1) where X is one with each adjacent carboxyl group Oxygen and/or polybasic acid unstable stabilizing epitopes form part of at least one acid labile bond; (ii) rhodium is a polymeric backbone epitope, which is selected from the group consisting of National Standard (CNS) A4 specification (210 X 297) 〉 1301928 A8 B8 C8 D8 The group consisting of a quantitative range of epitopes and a cyclic olefin epitope; (iii) Z is an epitope selected from a cycloalkyl group and a linear alkyl group (C 1 - C 3) in the group consisting of; · (iv) P is 〇 or 1; and * (v) Q is the larger end group; the acid generator is onium salt, six Hexafluoroarsenates, triflates, perfluoroalkane sulfonates, substituted aryl sulfonates, hydroxy sulfoximine sulfonates, N-sulfonyloxynaphthalimides, α-α 'bis-sulfonyl diazomethane, naphthoquinone- 4 - azide (naphthoquinone-4-diazide) or alkyl disulfone; wherein the composition comprises 〇 5 - 20% by weight of the acid to produce the weight percentage based on the total weight of the imaged polymer in the composition. Notes on the matters of the Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing 2, such as the scope of patent application The photoresist composition of the present invention, wherein the image forming polymer comprises (1) a cyclic olefin monomer unit which is located in the aforementioned polymer backbone; and/or (ii) a larger. volume alicyclic table Position, which is located at the end of the aforementioned PALM group. 3 · For the photoresist composition described in the scope of claim 1, the paper size on page 27 applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1301928 Α8 Β8 C8 D8, patent application The range contains palm polymerized dry epitopes. The monomer unit of the present invention comprises at least one cyclic olefinic bone, such as the photoresist composition of claim 1, wherein the monomer unit of the internal S PALM polymer contains at least one ethylene backbone epitope. The photoresist composition of claim 4, wherein the monomer unit of each of the PALM polymers comprises at least one thiol side group or trifluoroantimony side extending from the aforementioned ethylene backbone epitope. a group, the thiol side group or the trifluoromethyl side group and the PALM group are different in one place. The reading of the back of the note 4 of the Ministry of Economics, the Ministry of Economic Affairs, the Intellectual Property Office, the employee of the consumer cooperative, and the photo-resist composition of claim 1, wherein the image forming polymer further comprises at least one unit cell. The unit single system is selected from the group consisting of: a cyclic hydrocarbon monomer unit containing an acid labile epitope which inhibits the dissolution of the photoresist in the alkali aqueous solution in addition to the PALM group; (b) a cyclic olefin monomer containing a polar epitope capable of repairing a photoresist dissolved in an aqueous alkaline solution; (c) a cyclic olefin monomer containing a pendant lactone epitope; The monomer unit or the pendant group of the side group epitope is a non-polar and non-acid-labile cyclic dilute L monomer '(e) can be free-radically reacted with the aforementioned monomer unit containing a PALM group. Acyclic olefin monomer unit; and (1) acyclic second erroneous paper Chinese & Standard (CNS) Qiaoge (21 〇χ 297 gong) capable of undergoing addition polymerization with the aforementioned PALM group monomer unit stone

A8 B8 C8 D8 1301928 、申請專利範圍烯烴單體單元。 7·如中專利範圍第6項所述之光阻&成物，其中諸, 像聚合物至少包含（a)内含除p ALM基團以外之可抑^ 光阻在驗性水溶液巾溶解之酸不穩定表位的環狀心單體單元。 \ 8.如申凊專利範圍帛6項所述之光阻組成物，其中該) 像聚合物至少包含（b)内含可促進光阻在鹼性水溶·; 中溶解之極性表位的環狀烯烴單體。 9·如申請專利範圍第6項.所述之光阻組成物，其中該；像I C2物至少包含（c)内含内酯側基表位之環狀稀j 單體。〇·如申請專利範圍第6項所述之光阻組成物，其中該成像聚合物至少包含（e)可寒前述内含PAlm基團之單體單元進行自由基反應的非環狀烯烴單體單元。經濟部智慧財產局員工消費合作社印製 1 1 ·如申請專利範圍第6項所述之光阻組成物，其中該成像聚合物至少包含（f)可與前述内含palm基團單體單元進行加成聚合反應之非環狀烯烴單體單元。 12·如申請專利範圍第1項所述之光阻組成物，其中該成第29頁 ___: —_—_____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 1301928 i D8 六、申請專利範圍像聚s物包含至少20%莫耳百分比之内含palm基團之單體單元。 13. —種單體，其結構如下： Μ —ζ. ο ο ρ ο X 〇A8 B8 C8 D8 1301928, the scope of patent application olefin monomer unit. 7. The photoresist &amplifier of claim 6, wherein the image polymer comprises at least (a) a photo-resistance other than the p ALM group, which is soluble in the aqueous solution. A cyclic core monomer unit of an acid labile epitope. 8. The photoresist composition according to claim 6, wherein the image polymer comprises at least (b) a ring containing a polar epitope which promotes dissolution of the photoresist in the alkaline water solution; Olefin monomer. 9. The photoresist composition according to claim 6, wherein the I C2 material comprises at least (c) a cyclic rare monomer having a lactone side group epitope. The photoresist composition according to claim 6, wherein the image forming polymer comprises at least (e) a non-cyclic olefin monomer capable of undergoing a radical reaction of the monomer unit containing the PAlm group in the cold unit. The invention relates to a photoresist composition as claimed in claim 6, wherein the image forming polymer comprises at least (f) a monomer unit containing the palm group contained therein. Addition polymerization of acyclic olefin monomer units. 12. The photoresist composition as described in claim 1 of the patent application, wherein the page 29 ___: —_—_____ The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1301928 i D8 VI. The scope of the patent application is as a monomer unit containing a palm group containing at least 20% by mole of polys. 13. A monomer having the following structure: Μ —ζ. ο ο ρ ο X 〇

Q (請先Μ讀背面之注意事項Η π本頁) J-t 其中： (i) X為一可與每一鄰近羧基表位上的氧與/或内含多元酸不穩定表位本身形成至少一酸不穩定鍵之部分； . 經濟部智慧財產局員工消費合作社印製 (u) Μ為一聚合骨幹表位，其係分別選自由一乙烯表位與環狀烯烴表位所組成之群組中； (iii) Ζ為一種表位，其係選自由環烷基及直鍊烷基 (C 1 - C 3 )所組成之群組中； (iv) P為〇或1 ;及 (v) Q為一含有至少10個碳原子之具較大體積的末端基團，該末端基團係選自由環脂族表位及非第30頁本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐〉 1301928 六、申請專利範圍環狀飽和碳氫化合物所組成之群組中。 14. 一種可在一基材上形成一圖案化材料結構的方法，其中該材料係選自由半導體、陶瓷與金屬所組減之群組中，上述方法至少包含下列步驟： (A) 提供一種含有上述材料層之基材； (B) 將光阻組成物覆於上述基材上以形成一光阻層於該基材上，上述光阻組成物至少包含（a) 一成像聚合物；（b)—對光敏感的酸產生物；該成像聚合物至少包含單體單元，該單體單元係具有自.該單體中可聚合部分伸出之内含多元酸不穩定表位之側基團（PALM基團），該内含PALM基團之單體單元至少包含一含有至少 10個碳原子之具較大體積的末端基團，該末端基團係選自由環脂族表位及非環狀飽和碳氫化合物所組成之群組中，其中該 (請先¾讀背面之注意事項Η 頁) 經濟部智慧財產局員工消費合作社印製内含PALM單體單元具下列式之結構： -Μ-Q (please read the notes on the back Η π page) Jt where: (i) X is at least one of the oxygen and/or polyunsaturated unstable epitopes on each adjacent carboxyl epitope. Part of the acid labile bond; . Printed by the Intellectual Property Office of the Ministry of Economic Affairs, employee consumption cooperative (u) Μ is a polymeric backbone epitope, which is selected from the group consisting of an ethylene epitope and a cyclic olefin epitope. (iii) Ζ is an epitope selected from the group consisting of a cycloalkyl group and a linear alkyl group (C 1 - C 3 ); (iv) P is 〇 or 1; and (v) Q Is a larger volume of terminal groups containing at least 10 carbon atoms selected from the group consisting of cycloaliphatic epitopes and non-page 30 paper scales applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm> 1301928 6. In the group of patent-scoped cyclic saturated hydrocarbons. 14. A method of forming a patterned material structure on a substrate, wherein the material is selected from the group consisting of semiconductors and ceramics. In the group with metal reduction, the above method includes at least the following steps: (A) Providing a substrate comprising the above material layer; (B) coating a photoresist composition on the substrate to form a photoresist layer on the substrate, the photoresist composition comprising at least (a) an imaging polymer (b) a light-sensitive acid generator; the image forming polymer comprising at least a monomer unit having a polybasic acid unstable epitope extending from a polymerizable portion of the monomer a pendant group (PALM group), the monomer unit containing a PALM group comprising at least one terminal group having a larger volume containing at least 10 carbon atoms, the terminal group being selected from a cycloaliphatic epitope And the group consisting of acyclic saturated hydrocarbons, which should be (please read the back note Η page). The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, printed the PALM monomer unit with the following structure. : -Μ-

X 〇 I 'c=o Q 第31頁本紙張尺度適甩中國國家標準（CNS)A4規格（210 χ 297公釐〉 A8 B8 C8 D8 1301928 六、申請專利範圍其中 (請先閱讀背面之注意事項本頁) (i) X為一可與每一鄰近羧基表位上的氧與/或内含多元酸不穩定表位本身形成至少一酸不穩定鍵·之部分； (ii) Μ為一聚合骨幹表位，其係分別選自由一乙烯表位與環狀烯烴表位所組成之群組中； (iii) Z為一種表位，其係選自由環烧基及直鍊烧基 (C 1 - C 3)所組成之群組中； (iv) P為0或1 ;且 (v) Q為該具較大體積的末端基·團；該酸產生物係鏽鹽、六氟砷酸鹽.、三氟曱烷磺酸鹽、全氟烷基磺酸鹽、經取代之芳香基磺酸鹽、羥基醯亞胺的磺酸酯、N-磺醯氧基萘二甲醯亞胺、α — α，雙-磺醯基重氮甲烷、萘醌-4-疊氮或烷基雙砜；其中該組成物包含0.5-20%重量百分比的該酸產生物，該重量百分比係基於該組成物中該成像聚合物之總重量；經濟部智慧財產局員工消費合作社印製 (C) 以成像輻射光圖案化地曝嘩該基材，藉由光照使該光阻層的暴露區域中之該酸產生物產生酸；及 (D) 讓該基材與一鹼性顯影劑水溶液接觸，其中該光阻層上曝光部分可為該顯影溶液選擇性 . 地溶解，以露出該基材上經圖#化之光阻結構；及第3頂本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) A8 B8 C8 D8 1301928 申請專利範圍 (E)在上述光阻結構圖形之空間中，藉餘刻的方法將光阻結構圖形轉移到上述材料層。 15·如申請專利範圍第14項所述之方法，其中該材·料為金屬。 1 6·如申請專利範圍第1 4項所述之方法，其中該蝕刻至少包含反應性離子蝕刻。 . 1 7·如申請專利範圍第1 4項所述之方法，其中在上述材料層與上述光阻層中至少含有一種中間層，且步驟 (E)至少包含蝕刻穿過.上述中間層之步驟。 1 8·如申請專利範圍第1 4項所述之方法，其中該光之波長為193nm。 1 9 ·如申請專利範圍第丨4項所述之方法，其中該基材係於步驟（C)與（D)之間進行烘烤。經濟部智慧財產局員工消費合作社印製 20. —種光阻組成物，其至少包含（a)成像聚合物、.（b)對光敏感的酸產生物，其中前述之成像聚合物至少包含一單體單元，該單體單元係具有自單體中可聚合部分伸出之一内含多‘元酸不穩定表位之側基團 (PALM基團），其中該成像聚合物包含至少20%莫耳第33頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱〉經濟部智慧財產局員工消費合作社印製 4M 3 0 A8 1301928 1 六、申請專利範圍百分比之内含PALM基團之單體單元、及（c)一體積較大的疏水性添加物，其在波長為1 93 nm之輻射光下幾近透明。 · 21· —種光阻組成物，其至少包含（a)成像聚合物、與（b) 對光敏感的酸產生物，其中前述之成像聚合物至少包含一單體單元，該單體單元係具有自單體中可聚合部分伸出之一内含多元酸不穩定表位之側基團 (PALM基團），其中該成像聚合物包含至少20%莫耳百分比之内含PALM基團之單體單元。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉X 〇I 'c=o Q Page 31 This paper size is suitable for China National Standard (CNS) A4 specification (210 297 297 mm) A8 B8 C8 D8 1301928 VI. Patent application scope (please read the notes on the back first) (i) X is a moiety which forms at least one acid labile bond with the oxygen on the adjacent carboxyl group and/or the unstable polybasic epitope itself; (ii) Μ is a polymerization a backbone epitope selected from the group consisting of an ethylene epitope and a cyclic olefin epitope; (iii) Z is an epitope selected from a cycloalkyl group and a linear alkyl group (C 1 - C 3) in the group consisting of; (iv) P is 0 or 1; and (v) Q is the larger volume of terminal group; the acid generator is rust salt, hexafluoroarsenate ., trifluorosulfonate, perfluoroalkyl sulfonate, substituted aryl sulfonate, sulfonate of hydroxy quinone imine, N-sulfonyloxynaphthalene imine, α — α, bis-sulfonyldiazomethane, naphthoquinone-4-azide or alkyl disulfone; wherein the composition comprises 0.5-20% by weight of the acid generator, the weight percentage being based on The total weight of the imaged polymer in the composition; printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative (C), the substrate is patterned by imaging radiation, and exposed to the exposed area of the photoresist layer by illumination The acid generator generates an acid; and (D) contacting the substrate with an aqueous alkaline developer solution, wherein the exposed portion of the photoresist layer is selectively soluble in the developing solution to expose the substrate Figure #化的光阻结构; and the third top paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) A8 B8 C8 D8 1301928 Patent application scope (E) in the space of the above-mentioned photoresist structure pattern The method of transferring the photoresist structure to the material layer by the method of the invention. The method of claim 14, wherein the material is metal. 1 6 as claimed in claim 1 The method of claim 1, wherein the etching comprises at least one reactive layer etching, wherein the method of claim 14, wherein the material layer and the photoresist layer comprise at least one intermediate layer, And step (E The method of at least etching through the intermediate layer. The method of claim 14, wherein the wavelength of the light is 193 nm. 1 9 · as described in claim 4 The method, wherein the substrate is baked between steps (C) and (D). The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, printed 20. A photoresist composition comprising at least (a) imaging polymerization (b) a light-sensitive acid generator, wherein the aforementioned image forming polymer comprises at least one monomer unit having a plurality of 'acids' extending from the polymerizable portion of the monomer The side group of the unstable epitope (PALM group), wherein the imaging polymer contains at least 20% Molar page 33. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) Property Bureau Staff Consumer Cooperatives Print 4M 3 0 A8 1301928 1 6. Monomer units containing PALM groups in percentage of patent applications, and (c) a bulky hydrophobic additive at a wavelength of 1 93 The radiation of nm is almost transparent. A photoresist composition comprising at least (a) an imaging polymer, and (b) a light-sensitive acid generator, wherein the image forming polymer comprises at least one monomer unit, the monomer unit a pendant group (PALM group) having a polybasic acid labile epitope extending from a polymerisable moiety in the monomer, wherein the imaging polymer comprises at least 20% molar percentage of a PALM-containing group Body unit. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)